Additive for an electrolyte solution for an electrochemical device

ABSTRACT

There is provided a lithium secondary battery which has excellent characteristics such as energy density and electromotive force and is excellent in cycle life and storage stability. An electrolyte solution for secondary battery comprising at least an aprotic solvent having an electrolyte dissolved therein and a compound represented by the general formula (1).

This is a 371 National Stage application of International applicationno. PCT/JP2004/018698, filed Dec. 14, 2004, which claims priority toJapanese Application Nos. 2003-416516, filed Dec. 15, 2003 and2004-317301, filed Oct. 29, 2004. The entire contents of theabove-referenced applications are hereby incorporated by reference intheir entirety.

TECHNICAL FIELD

The present invention relates to an additive used for an electrolytesolution for an electrochemical device, an electrolyte solution forsecondary battery and a secondary battery using the same.

BACKGROUND ART

A non-aqueous electrolyte solution type lithium-ion or lithium secondarybattery in which a carbon material or lithium metal is used in an anodewhile a lithium-containing complex oxide is used in a cathode has drawnattention as an electric source for a cellular phone, a notebookcomputer or the like because it can realize a higher energy density. Itis generally known that in such a secondary battery, a film which iscalled a surface film, a protective film, an SEI or a membrane is formedon an electrode surface. It is also well-known that controlling thesurface film is essential for improving electrode performance becausethe surface film significantly influences a charge/discharge efficiency,a cycle life and safety. Specifically, when using a carbon material asan anode material, its irreversible capacity must be reduced, and in alithium-metal anode, a charge/discharge efficiency must be reduced whilea safety problem due to dendrite formation must be solved.

There have been suggested a variety of procedures for solving theproblems. For example, there has been suggested that a membrane layermade of, e.g., lithium fluoride is formed on a surface of lithium metalby a chemical reaction when using lithium metal as the anode material,to minimize formation of dendrites.

Japanese Patent Application No. 1995-302617 has disclosed that a lithiumanode is exposed to an electrolyte solution containing hydrofluoric acidfor initiating a reaction of the anode with hydrofluoric acid to coatthe surface with a lithium fluoride film. Hydrofluoric acid is generatedby a reaction of LiPF₆ with a small amount of water. On the other hand,a surface film of lithium hydroxide or lithium oxide is formed on thesurface of the lithium anode by autoxidation in the air. These react toform a surface film of lithium fluoride on the anode surface. However,since the lithium fluoride film is formed by utilizing a reaction of anelectrode interface with a liquid, the surface film may tend to becontaminated with byproducts, leading to an uneven film. Sometimes, asurface film of lithium hydroxide or lithium oxide may not be formed asan even film or in some area lithium metal may be exposed. Such casesmay lead to not only an uneven film, but also a safety problem due to areaction of lithium with water or hydofluoric acid. An insufficientreaction may lead to a residue of undesired compounds other thanfluoride, which may be harmful by causing reduction in anionconductivity. Furthermore, in a process for forming a fluoride layerutilizing a chemical reaction in such an interface, there arelimitations to fluorides or electrolyte solutions which can be used. Itis, therefore, difficult to form a stable surface film in a good yield.

In Japanese Patent Application No. 1996-250108, a mixed gas of argon andhydrogen fluoride is reacted with an aluminum-lithium alloy to form asurface film of lithium fluoride on an anode surface. However, if apreformed surface film is present on the surface of lithium metal, inparticular if a plurality of components are present, the reaction tendsto be uneven, which may make it difficult to form an even lithiumfluoride film. In such a case, a lithium secondary battery exhibitingsatisfactory cycle properties cannot be obtained.

Japanese Patent Application No. 1999-288706 has disclosed that a surfacemembrane structure comprising a substance with a rock-salt type crystalstructure as a main component is formed on a lithium sheet in which aneven crystal structure, i.e., a (100) crystal face, is preferentiallyoriented. It has been thus described that an evenprecipitation/dissolution reaction, i.e., an even batterycharge/discharge can be achieved, resulting in prevention of dendriteprecipitation of lithium and improvement in a battery cycle life. Asubstance used in a surface film preferably comprises a lithium halide,which is preferably comprised of at least one selected from the groupconsisting of LiCl, LiBr and Lil and its solid solution with LiF.Specifically, for forming a solid solution membrane of at least oneselected from the group consisting of LiCl, LiBr and Lil with LiF, alithium sheet formed by pressing (rolling) in which a (100) crystal faceis preferentially oriented is immersed in an electrolyte solutioncontaining at least one selected from group consisting of (1) chlorinemolecules or chloride ions, (2) bromine molecules or bromide ions, and(3) iodine molecules or iodide ions and containing fluorine molecules orfluoride ions to form an anode for a non-aqueous electrolyte battery. Inthis technique, an rolled lithium metal sheet is used. Since the lithiumsheet tends to be exposed in the air, a membrane derived from moistureand so on may be formed on its surface, leading to uneven distributionof active sites. It may be, therefore, difficult to form a desiredstable surface film. Thus, this technique has not always been effectivefor adequately preventing dendrite formation.

There has been described a technique that a capacity and acharge/discharge efficiency can be improved when using as an anode acarbon material such as graphite and hard carbon in which lithium ionscan be occluded and released.

Japanese Patent Application No. 1993-234583 has suggested an anode wherea carbon material is coated with aluminum, whereby reductivedecomposition of a solvent molecule in a solvate with a lithium ion onthe carbon surface is reduced to minimize reduction in a cycle life.However, since aluminum reacts with a small of moisture, repeated cyclesmay lead to rapid reduction in a capacity.

Japanese Patent Application No. 1993-275077 has suggested an anode inwhich a carbon material surface is coated with a film of a lithium-ionconductive solid electrolyte, whereby decomposition of a solvent whenusing a carbon material can be minimized, so that a lithium ionsecondary battery which particularly allows propylene carbonate to beused can be provided. However, change of stress during insertion andremoval of lithium ions generates cracks in the solid electrolyte, whichmay lead to deteriorated properties. Due to unevenness such as crystaldefects in the solid electrolyte, an even reaction cannot be achieved inthe anode surface, sometimes leading to a reduced cycle life.

Japanese Patent Application No. 2000-3724 has disclosed a secondarybattery wherein an anode is made of a graphite-containing material andan electrolyte solution comprises a cyclic and linear carbonate as amain component and 0.1 weight % to 4 weight % both inclusive of1,3-propanesultone and/or 1,4-butanesultone as a cyclic monosulfonate inthe electrolyte solution. It is believed that 1,3-propanesultone or1,4-butanesultone contributes to formation of a passive membrane on acarbon material surface, which can coat an active and highlycrystallized carbon material such as natural or artificial graphite withthe passive membrane to prevent decomposition of an electrolyte solutionwithout deterioration of a normal reaction in a battery. Japanese PatentApplication No. 2000-133304 and U.S. Pat. No. 6,436,582B1 have describedthat in addition to a cyclic monosulfonate, a linear disulfonate may besimilarly effective. However, using the cyclic monosulfonate in JapanesePatent Application No. 2000-3724 or the linear disulfonate in JapanesePatent Application No. 2000-133304 and U.S. Pat. No. 6,436,582B1, amembrane may be formed mainly on an anode while forming a membrane on,for example, a cathode may be substantially difficult. In addition,Japanese Patent Application No. 1993-44946 and U.S. Pat. No. 4,950,768B1has disclosed a process for preparing a cyclic sulfonate having twosulfonyl groups. J. Am. Pham. Assoc., Vol. 126, pp. 485-493 (1937) andG. Schroeter, Lieb, Ann, Der Chemie, Vol. 418, pp. 161-257 (1919) andBiol. Aktiv. Soedin., pp. 64-69 (1968), Armyanskii Khimicheskii Zhurnal,21, pp. 393-396 (1968) has disclosed a process for preparing a linearsulfonate.

In Japanese Patent Application No. 2003-7334, an aromatic compound isadded to a solvent for an electrolyte solution for preventing oxidationof the solvent for an electrolyte solution to minimize deterioration ina capacity after long-term repetition of charge/discharge of a secondarybattery. It is a technique for preventing solvent decomposition bypreferentially decomposing the aromatic compound by oxidation. However,when using the additive, sometimes a cathode surface is not coated,resulting in insufficient improvement in cycle properties.

Japanese Patent Application No. 2003-115324 has described that anitrogen-containing unsaturated cyclic compound is added to anelectrolyte solution to improve cycle properties when using ahigh-voltage cathode. However, while the nitrogen-containing unsaturatedcyclic compound can improve a charge/discharge efficiency in an anode,it cannot improve a charge/discharge efficiency in a cathode.

DISCLOSURE OF THE INVENTION

The related art have the following problems in common. Although thesurface film generated on the surface of the electrodes has deepinfluence on charge/discharge efficiency, cycle life and safetydepending on their properties, the related art forms a stabilized filmmainly on the anode, and no techniques to stably form films on both ofthe anode and the cathode have been disclosed.

In addition, as for the conventionally used techniques to form a film onthe cathode, there has been no technique to enable control of the filmover a long period of time. For this reason, although an effect ofsuppressing dendrite could be obtained to a certain extent at theinitial use, when it was used repeatedly, the surface film might beimpaired to deteriorate the function as a protection film. This isconsidered to be attributable to the fact that the occlusion and releaseof lithium cause changes in volume of the layer of cathode activematerial containing the lithium while the film formed on the surfacethereof scarcely changes in volume and therefore, internal stress occurswithin these layers and the interface therebetween. When such internalstress occurs, the surface film is partly damaged, which is supposed tocause deterioration of dendrite suppressing function. This leads todecomposition of the electrolyte solution and consequently it has beendifficult to maintain high discharge capacity and excellent cyclecharacteristic.

Furthermore, even if the conventional technique was used, when carbonmaterials such as graphite were used for anode, there were cases whereelectric charge resulted from decomposition of the solvent molecules oranions appeared as an irreversible capacity component, and causeddecrease in the initial charge/discharge efficiency. The composition,crystal state, stability, etc. of the film resulted at this stage maysignificantly adversely affect the subsequent efficiency and the cyclelife.

As mentioned above, researches have been conducted aiming at improvingcharge/discharge efficiency, cycle life and so on by forming a film onthe electrode for a secondary battery but films cannot be stably formedon the electrodes (both cathode and anode) and generally, sufficientbattery characteristics have not been achieved yet.

The present invention has been made in view of the problems, and theinvention forms stabilized films on the surface of electrodes (bothcathode and anode) by adding a linear disulfonate in the electrolytesolution for secondary battery and prevents decomposition of thecomponents of the electrolyte solution. Consequently, the invention alsoaims at providing a secondary battery excellent in cycle characteristicor charge/discharge efficiency.

In order to solve the problems, the present invention has the followingconstruction. That is, the present invention relates to an electrolytesolution for secondary battery comprising at least an aprotic solventhaving an electrolyte dissolved therein and a compound represented bythe following general formula (1):

wherein R₁ and R₄ independently represent an atom or a group selectedfrom a hydrogen atom, a substituted or unsubstituted alkyl group having1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having1 to 5 carbon atoms, a substituted or unsubstituted fluoroalkyl grouphaving 1 to 5 carbon atoms, a polyfluoroalkyl group having 1 to 5 carbonatoms, —SO₂X₁, wherein X₁ is a substituted or unsubstituted alkyl grouphaving 1 to 5 carbon atoms, —SY₁, wherein Y₁ is a substituted orunsubstituted alkyl group having 1 to 5 carbon atoms, —COZ, wherein Z isa hydrogen atom or a substituted or unsubstituted alkyl group having 1to 5 carbon atoms, and a halogen atom; and R₂ and R₃ independentlyrepresent an atom or a group selected from a substituted orunsubstituted alkyl group having 1 to 5 carbon atoms, a substituted orunsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted orunsubstituted phenoxy group, a substituted or unsubstituted fluoroalkylgroup having 1 to 5 carbon atoms, a polyfluoroalkyl group having 1 to 5carbon atoms, a substituted or unsubstituted fluoroalkoxy group having 1to 5 carbon atoms, a polyfluoroalkoxy group having 1 to 5 carbon atoms,a hydroxyl group, a halogen atom, —NX₂X₃, wherein X₂ and X₃independently represent a hydrogen atom or a substituted orunsubstituted alkyl group having 1 to 5 carbon atoms, and —NY₂CONY₃Y₄,wherein Y₂ to Y₄ independently represent a hydrogen atom or asubstituted or unsubstituted alkyl group having 1 to 5 carbon atoms.

Furthermore, it is preferable in the present invention that the compoundrepresented by the general formula (1) is contained in the electrolytesolution for secondary battery in an amount of 0.1 to 5.0 weight % basedon the total weight of the electrolyte solution for secondary battery.

Furthermore, it is preferable in the present invention that theelectrolyte solution for secondary battery further comprises a cyclicmonosulfonate represented by the following general formula (2):

wherein n is an integer of 0 to 2; R₅ to R₁₀ independently represent anatom or a group selected from a hydrogen atom, a substituted orunsubstituted alkyl group having 1 to 12 carbon atoms, a substituted orunsubstituted fluoroalkyl group having 1 to 6 carbon atoms, and apolyfluoroalkyl group having 1 to 6 carbon atoms.

Furthermore, it is preferable in the present invention that theelectrolyte solution for secondary battery further comprises a cyclicsulfonate having two sulfonyl groups represented by the followinggeneral formula (3):

wherein Q represents an oxygen atom, an methylene group or a singlebond, A represents a group selected from a substituted or unsubstitutedalkylene group having 1 to 5 carbon atoms, a carbonyl group, a sulfinylgroup, a polyfluoroalkylene group having 1 to 5 carbon atoms, asubstituted or unsubstituted fluoroalkylene group having 1 to 5 carbonatoms, a substituted or unsubstituted alkylene group having 1 to 5carbon atoms in which at least one of C—C bonds is converted into aC—O—C bond, a polyfluoroalkylene group having 1 to 5 carbon atoms inwhich at least one of C—C bonds is converted into a C—O—C bond, and asubstituted or unsubstituted fluoroalkylene group having 1 to 5 carbonatoms in which at least one of C—C bonds is converted into a C—O—C bond;and B represents a group selected from a substituted or unsubstitutedalkylene group having 1 to 5 carbon atoms, a polyfluoroalkylene grouphaving 1 to 5 carbon atoms, and a substituted or unsubstitutedfluoroalkylene group having 1 to 5 carbon atoms.

Furthermore, it is preferable in the present invention that theelectrolyte solution for secondary battery further comprises at leastone of vinylene carbonate and derivative thereof.

Furthermore, it is preferable in the present invention that theelectrolyte solution for secondary battery comprises a lithium salt, andit is preferable that the lithium salt is at least one lithium saltselected from the group consisting of LiPF₆, LiBF₄, LiAsF₆, LiSbF₆,LiClO₄, LiAlCl₄, and LiN(C_(k)F_(2k+1)SO₂)(C_(m)F_(2m+1)SO₂), wherein kand m are independently 1 or 2.

Furthermore, it is preferable in the present invention that the aproticsolvent is at least one organic solvent selected from the groupconsisting of cyclic carbonates, linear carbonates,aliphatic-carboxylates, γ-lactones, cyclic ethers, linear ethers andfluoride derivatives thereof.

Furthermore, it is preferable in the present invention that a secondarybattery has a cathode, an anode and an electrolyte solution forsecondary battery in which the electrolyte solution for secondarybattery is preferably the electrolyte solution for secondary battery.

Furthermore, it is preferable in the present invention that the anodecomprises lithium metal or carbon as an anode active material.

Furthermore, it is preferable in the present invention that the anodecomprises graphite or amorphous carbon as the carbon.

Furthermore, the present invention is preferably characterized in thatthe secondary battery is covered with a laminate jacket.

In addition, the present invention relates to an additive forelectrolyte solution for an electrochemical device which comprises acompound represented by the following general formula (1).

wherein R₁ and R₄ independently represent an atom or a group selectedfrom a hydrogen atom, a substituted or unsubstituted alkyl group having1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having1 to 5 carbon atoms, a substituted or unsubstituted fluoroalkyl grouphaving 1 to 5 carbon atoms, a polyfluoroalkyl group having 1 to 5 carbonatoms, —SO₂X₁, wherein X₁ is a substituted or unsubstituted alkyl grouphaving 1 to 5 carbon atoms, —SY₁, wherein Y₁ is a substituted orunsubstituted alkyl group having 1 to 5 carbon atoms, —COZ, wherein Z isa hydrogen atom or a substituted or unsubstituted alkyl group having 1to 5 carbon atoms, and a halogen atom; and R₂ and R₃ independentlyrepresent an atom or a group selected from a substituted orunsubstituted alkyl group having 1 to 5 carbon atoms, a substituted orunsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted orunsubstituted phenoxy group, a substituted or unsubstituted fluoroalkylgroup having 1 to 5 carbon atoms, a polyfluoroalkyl group having 1 to 5carbon atoms, a substituted or unsubstituted fluoroalkoxy group having 1to 5 carbon atoms, a polyfluoroalkoxy group having 1 to 5 carbon atoms,a hydroxyl group, a halogen atom, —NX₂X₃, wherein X₂ and X₃independently represent a hydrogen atom or a substituted orunsubstituted alkyl group having 1 to 5 carbon atoms, and —NY₂CONY₃Y₄,wherein Y₂ to Y₄ independently represent a hydrogen atom or asubstituted or unsubstituted alkyl group having 1 to 5 carbon atoms.

In this specification the terms “polyfluoroalkylene group”,“polyfluoroalkyl group” and “polyfluoroalkoxy group” representcorresponding alkylene group, alkyl group and alkoxy group,respectively, in which all the hydrogen atoms bonded to carbon atom aresubstituted with fluorine atoms, and the terms “fluoroalkylene group”,“fluoroalkyl group” and “fluoroalkoxy group” represent correspondingalkylene group, alkyl group and alkoxy group, respectively, in which apart of the hydrogen atoms bonded to carbon atom are substituted withfluorine atom(s).

Furthermore, the term “substituted” in “substituted fluoroalkylenegroup”, “substituted fluoroalkyl group” and “substituted fluoroalkoxygroup” represents that at least one of the hydrogen atoms bonded tocarbon atom is substituted with an atom or a functional group other thanfluorine. The atom or functional group other than fluorine can be, forexample, a halogen atom such as a chlorine atom, a bromine atom and aniodine atom, a hydroxyl group, or an alkoxy group having 1 to 5 carbonatoms or a group substituted with a group such as a halogen atom or ahydroxyl group, or a group into which —SO₂— is introduced (for example,—OSO₂CH₂SO₂Cl). When a carbon atom is contained in this functionalgroup, this carbon atom shall not be contained in the number of “1 to 5carbon atoms” in the description of “a substituted or unsubstitutedalkyl group having 1 to 5 carbon atoms” and the like.

According to the present invention, an electrolyte solution forsecondary battery which contains a linear disulfonate of the presentinvention in an aprotic solvent is used, and the thus obtained secondarybattery is excellent in charge/discharge efficiency, good in cyclecharacteristics and provides an excellent lithium secondary batterywhich has a high capacity retention ratio and enables suppression ofincrease in resistance during storage.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view illustrating the structure of the secondarybattery of the present invention.

DESCRIPTION OF SYMBOLS

Explanations of Letters of Numerals

-   11 Cathode current collector-   12 Layer comprising cathode active material-   13 Layer comprising anode active material-   14 Anode current collector-   15 Non-aqueous electrolyte solution-   16 Porous separator

BEST MODE FOR CARRYING OUT THE INVENTION

(Description of the Battery Construction by the Present Invention)

FIG. 1 shows an outlined structure of a battery according to the presentinvention, which is composed of a cathode current collector 11, a layer12 comprising the cathode active material which can occlude and releaselithium ions, a layer 13 comprising the anode active material whichoccludes and releases lithium ions, an anode current collector 14, anelectrolyte solution 15 and a separator 16. Here, the linear disulfonicacid compound (linear disulfonate) represented by the general formula(1) is contained in the electrolyte solution 15.

(Current Collector)

As the cathode current collector 11, aluminum, stainless steel, nickel,titanium or an alloy thereof can be used, and as the anode currentcollector 14, copper, stainless steel, nickel, titanium an alloy thereofcan be used.

(Separator)

As the separator 16, a porous film such as polyolefin such aspolypropylene and polyethylene, and a fluororesin can be preferablyused.

(Cathode)

Lithium containing composite oxides usually used can be used as thecathode active material, and specifically materials such as LiMO₂,wherein M is selected from Mn, Fe and Co which may be partiallysubstituted with a cation such as Mg, Al, Ti, etc., and LiMn₂O₄. Thelayer 12 which serves as a cathode can be obtained by a method of usinga selected cathode active material, distributing and mixing it with aconductive material such as carbon black and a binder such aspolyvinylidene fluoride (PVDF) in a solvent such asN-methyl-2-pyrrolidone (NMP), and applying this on the substrate such asan aluminum foil.

(Anode)

The anode active material is composed of lithium metal or a materialwhich can occlude and release lithium such as a carbon material. As acarbon material, graphite, amorphous carbon, diamond-like carbon,fullerene, carbon nanotube, carbon nanohorn, etc. or a compositematerial thereof which can occlude lithium can be used. When lithiummetal is used as an anode active material, the layer 13 which serves asanode can be obtained by an appropriate method such as a melt coolingmethod, a liquid rapid cooling method, an atomization method, a vacuumvapor deposition method, a sputtering method, a plasma CVD method, aphoto CVD method (photo chemical vapor deposition), a thermal CVD and asol-gel method. When a carbon material is used, the layer 13 whichserves as anode can be obtained by mixing the carbon and a binder suchas polyvinylidene fluoride (PVDF), then distributing and mixing in asolvent such as NMP followed by applying the mixture on a substrate suchas a copper foil method, or a vapor deposition method, a CVD method, asputtering method.

(Electrolyte Solution)

The electrolyte solution 15 comprises an electrolyte, an aprotic solventand an additive at least.

(Electrolyte)

In the case of a lithium secondary battery, a lithium salt is used asthe electrolyte and dissolved in an aprotic solvent. The lithium saltincludes lithium imide salts, LiPF₆, LiAsF₆, LiAlCl₄, LiClO₄, LiBF₄,LiSbF₆, etc. Among these, LiPF₆ and LiBF₄ are preferable. The lithiumimide salt includes LiN(C_(k)F_(2k+1)SO₂)(C_(m)F_(2m+1)SO₂), wherein kand m are 1 or 2 independently. These can be used alone or incombination of two or more. High energy density can be attained whensuch a lithium salt is contained.

(Aprotic Solvent)

As an aprotic electrolyte solution, at least one of organic solventsselected from cyclic carbonates, linear carbonates,aliphatic-carboxylates, γ-lactone, cyclic ether, linear ether, andfluoride derivatives thereof is used. More specifically, one or two ormore thereof as a mixture of the following solvents can be used:

-   Cyclic carbonates: propylene carbonate (hereinafter abbreviated as    PC), ethylene carbonate (hereinafter abbreviated as EC), butylene    carbonate (BC) and the derivatives thereof;-   Linear carbonates: dimethyl carbonate (DMC), diethyl carbonate    (hereinafter abbreviated as DEC), ethyl methyl carbonate (EMC),    dipropyl carbonate (DPC) and the derivatives thereof;-   Aliphatic-carboxylates: methyl formate, methyl acetate, ethyl    propionate and the derivatives thereof;-   γ-lactones: γ-butyrolactone and the derivatives thereof;-   Cyclic ethers: tetrahydrofuran, 2-methyltetrahydrofuran and the    derivatives thereof;-   Linear ethers: 1,2-diethoxyethane (DEE), ethoxymethoxyethane (EME),    diethyl ether, and the derivatives thereof;-   Others: dimethylsulfoxide, 1,3-dioxolan, formamide, acetamide,    dimethylformamide, acetonitrile, propionitrile, nitromethane,    ethylmonoglyme, phosphotriester, trimethoxymethane, dioxolan    derivatives, methylsulfolane, 1,3-dimethyl-2-imidazolidinone,    3-methyl-2-oxazolidinone, anisole, N-methylpyrrolidone, fluoride    carboxylate.    (Additives)

As an additive, the linear disulfonate represented by the generalformula (1) is used.

wherein R₁ and R₄ independently represent an atom or a group selectedfrom a hydrogen atom, a substituted or unsubstituted alkyl group having1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having1 to 5 carbon atoms, a substituted or unsubstituted fluoroalkyl grouphaving 1 to 5 carbon atoms, a polyfluoroalkyl group having 1 to 5 carbonatoms, —SO₂X₁, wherein X₁ is a substituted or unsubstituted alkyl grouphaving 1 to 5 carbon atoms, —SY₁, wherein Y₁ is a substituted orunsubstituted alkyl group having 1 to 5 carbon atoms, —COZ, wherein Z isa hydrogen atom or a substituted or unsubstituted alkyl group having 1to 5 carbon atoms, and a halogen atom; and R₂ and R₃ independentlyrepresent an atom or a group selected from a substituted orunsubstituted alkyl group having 1 to 5 carbon atoms, a substituted orunsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted orunsubstituted phenoxy group, a substituted or unsubstituted fluoroalkylgroup having 1 to 5 carbon atoms, a polyfluoroalkyl group having 1 to 5carbon atoms, a substituted or unsubstituted fluoroalkoxy group having 1to 5 carbon atoms, a polyfluoroalkoxy group having 1 to 5 carbon atoms,a hydroxyl group, a halogen atom, —NX₂X₃, wherein X₂ and X₃independently represent a hydrogen atom or a substituted orunsubstituted alkyl group having 1 to 5 carbon atoms, and —NY₂CONY₃Y₄,wherein Y₂ to Y₄ independently represent a hydrogen atom or asubstituted or unsubstituted alkyl group having 1 to 5 carbon atoms.

The compound represented by the general formula (1) is an acycliccompound and can be synthesized without cyclization reaction at the timeof synthesis, for example by following J. Am. Pham. Assoc., vol. 126,pp. 485-493 (1937); G. Schroeter, Lieb, Ann, Der Chemie, vol. 418, pp.161-257 (1919); Biol. Aktiv. Soedin., pp 64-69 (1968); ArmyanskiiKhimicheskii Zhurnal, 21, pp. 393-396 (1968). In addition, the compoundcan also be obtained as a by-product of the synthesis of cyclicsulfonates having two sulfonyl groups disclosed in Japanese PatentPublication Japanese Patent Application No. 1993-44946. The compoundrepresented by the general formula (1) can be synthesized by easyprocesses, it has an advantage that an inexpensive electrolyte solutioncan be provided.

As for the preferable molecule structure, each of R₁ and R₄ of thegeneral formula (1) is independently an atom or a group selected from ahydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atomand —SO₂X₁, wherein X₁ is a substituted or unsubstituted alkyl grouphaving 1 to 5 carbon atoms, more preferably independently a hydrogenatom, an unsubstituted alkyl group having 1 to 5 carbon atoms, and stillmore preferably independently a hydrogen atom or a methyl group from theviewpoint including readiness of formation of a reactive film whichoccurs on the electrodes, stability of the compound, easiness ofhandling, solubility in a solvent, easiness of synthesis of the compoundand cost. The particularly preferable form of R₁ and R₄ is the casewhere R₁ and R₄ are hydrogen atoms. If R₁ and R₄ are hydrogen atoms, themethylene moiety between the two sulfonyl groups is activated and itbecomes easy to form the reaction film on the electrodes.

As for R₂ and R₃, each of R₂ and R₃ is independently an atom or a groupselected from a substituted or unsubstituted alkyl group having 1 to 5carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5carbon atoms, a substituted or unsubstituted phenoxy group, a hydroxylgroup, a halogen atom, and —NX₂X₃, wherein X₂ and X₃ independentlyrepresent a hydrogen atom, a substituted or unsubstituted alkyl grouphaving 1 to 5 carbon atoms, more preferably independently a substitutedor unsubstituted alkyl group having 1 to 5 carbon atoms, a substitutedor unsubstituted alkoxy group having 1 to 5 carbon atoms, and still morepreferably independently either one or both of R₂ and R₃ are substitutedor unsubstituted alkoxy groups having 1 to 5 carbon atoms from theviewpoint including stability of the compound, easiness of synthesis ofthe compound, solubility in a solvent and cost. For the same reason, thesubstituted or unsubstituted alkyl group having 1 to 5 carbon atoms ispreferably a methyl group or an ethyl group, and the substituted orunsubstituted alkoxy group having 1 to 5 carbon atoms is a methoxy groupor an ethoxy group.

The compound of the general formula (1) has two sulfonyl groups, whichmeans that the LUMO thereof is low, and since the compound has LUMO witha value lower than that of the solvent molecule in electrolyte solution,monosulfonate, it is readily reduced. For example, according tosemiempirical molecular orbital calculation, LUMO of Compound No. 1shown in the following table 1 is as low as −0.86 eV. Therefore, thereduced film of Compound No.1 is presumably formed on the anode prior tothe solvent (LUMO: about 1.2 eV) which comprises a cyclic carbonate orlinear carbonate, and the reduced film functions to suppress thedecomposition of the solvent molecule. Since the decomposition of thesolvent molecule is suppressed and the decomposition film of the solventmolecule having a high resistance is hard to be formed on the anode,suppression of increase in resistance and improvement in the cyclecharacteristics can be expected. It is also supposed that the structurein which two electron-withdrawing sulfonyl groups bind to a carbon atommay activate the carbon atom and promote the film formation on theelectrode. Furthermore, it supposed that a carb anion generated bydeprotonation of the activated methylene may coordinate to Li or reactto form a film on the cathode. Specific examples of the general formula(1) are shown below, but the present invention is not particularlylimited to these.

Although not particularly limited, the compound represented by thegeneral formula (1) is preferably contained in an amount of 0.1 weight %to 5.0 weight % in the electrolyte solution. The effect may not besufficiently exhibited below 0.1 weight % in the film formation throughelectrochemical reaction on the surface of the electrodes. If it exceeds5.0 weight %, the compound is not only hard to be dissolved, but mayincrease the viscosity of the electrolyte solution. More preferably, thecompound is added in a range of 0.5 weight % to 3.0 weight % in thepresent invention, which results in more sufficient film coating effect.

One compound represented by the general formula (1) may be used alone ortwo or more of them may be used in combination. When two or more of themare used in combination, although not particularly limited, it iseffective from a viewpoint of the easiness of film formation on theelectrodes that at least one compound having an active methylene group(that is, a compound in which R₁ and R₄ are hydrogen atoms) iscontained. As a specific combination, they are compounds of the CompoundNo.1 (compound which has an active methylene group) and Compound No.5.

When two or more kinds of compounds of the general formula (1) are addedto the electrolyte solution, although the ratio thereof in theelectrolyte solution is not particularly limited, the two as a whole arepreferably contained in an amount of 0.1 weight % to 5.0 weight % forthe same reason as above. In addition, when two or more kinds ofcompounds of the general formula (1) are added, although the ratio ofeach compound to the total weight of the compounds of the generalformula (1) is not particularly limited but it is preferable that thecontent of the least contained compound is 5 weight % and the content ofthe most contained compound is 95 weight %.

Furthermore, it is also effective to use an electrolyte solution whichcontains at least one of cyclic monosulfonates, cyclic sulfonates havingtwo sulfonyl groups, alkane sulfonic anhydrides and sulfolene compoundsin the electrolyte solution containing the compound of the generalformula (1).

The cyclic monosulfonate include a compound represented by the followinggeneral formula (2):

wherein n is an integer of 0 to 2; R₅ to R₁₀ independently represent anatom or a group selected from a hydrogen atom, a substituted orunsubstituted alkyl group having 1 to 12 carbon atoms, a substituted orunsubstituted fluoroalkyl group having 1 to 6 carbon atoms, and apolyfluoroalkyl group having 1 to 6 carbon atoms.

From the viewpoint including stability of the compound, easiness ofsynthesis of the compound, solubility in a solvent and cost, n ispreferably 0 or 1, and R₅ to R₁₀ preferably independently represent aatom or a group selected from a hydrogen atom, a substituted orunsubstituted alkyl group having 1 to 12 carbon atoms and apolyfluoroalkyl group having 1 to 5 carbon atoms, and more preferablyindependently represent a hydrogen atom or a polyfluoroalkyl grouphaving 1 to 5 carbon atoms in the compound represented by the generalformula (2). Still more preferably, all of R₅ to R₁₀ are hydrogen atoms,or one or two of R₅ to R₁₀ are polyfluoroalkyl groups having 1 to 5carbon atoms and the others are hydrogen atoms. As a polyfluoroalkylgroup having 1 to 5 carbon atoms mentioned above, trifluoromethyl groupis preferable.

Specific examples thereof include 1,3-propane sultone (1,3-PS),α-trifluoromethyl-γ-sultone, β-trifluoromethyl-γ-sultone,γ-trifluoromethyl-γ-sultone, α-methyl-γ-sultone,α,β-di(trifluoromethyl)-γ-sultone, α,α-di(trifluoromethyl)-γ-sultone,α-undecafluoropentyl-γ-sultone, α-heptafluoropropyl-γ-sultone,1,4-butane sultone (1,4-BS), etc.

It is considered that among these, 1,3-propane sultone (1,3-PS) forms adecomposition film on the anode of a secondary lithium-ion battery. LUMOof 1,3-PS is 0.07 eV, and is higher than that of Compound No.1 of thepresent invention (−0.86 eV). For example, when Compound No.1 of thepresent invention and 1,3-PS are added in the electrolyte solution andelectrically charged, it is considered that the substance of CompoundNo.1 forms a film on the anode first, and then 1,3-PS forms a film.Although a part of the anode surface mainly reacts and Compound No.1 atthe initial stage of charging, charging proceeds on the part which hasnot been reacted with the Compound No.1 (the part which is possible toreact with a solvent molecule) where reaction with 1,3-PS occurs, andconsequently a composite film of Compound No.1 and 1,3-PS is formed, theeffects of suppressing further increase in the resistance and swell ofbattery, etc. can be expected.

When the compound of the general formula (2) is added in the electrolytesolution, the content thereof in the electrolyte solution is notparticularly limited but it is preferably contained in an amount of 0.5weight % to 10.0 weight % in the electrolyte solution. The effect maynot be sufficiently exhibited below 0.5 weight % in the film formationthrough electrochemical reaction on the surface of the electrodes. If itexceeds 10.0 weight %, the viscosity of the electrolyte solution mayincrease. The ratio of the compound of the general formula (2) in thecompounds of the general formula (1) and the general formula (2) ispreferably 10 to 90 weight % based on the total weight of the compoundof the general formula (1) and the compound of the general formula (2),respectively.

The cyclic sulfonate having two sulfonyl groups include a compoundrepresented by the following general formula (3):

wherein Q represents an oxygen atom, an methylene group or a singlebond, A represents a group selected from a substituted or unsubstitutedalkylene group having 1 to 5 carbon atoms, a carbonyl group, a sulfinylgroup, a polyfluoroalkylene group having 1 to 5 carbon atoms, asubstituted or unsubstituted fluoroalkylene group having 1 to 5 carbonatoms, substituted or unsubstituted alkylene group having 1 to 5 carbonatoms in which at least one of C—C bonds is converted into a C—O—C bond,a polyfluoroalkylene group having 1 to 5 carbon atoms in which at leastone of C—C bonds is converted into a C—O—C bond, and a substituted orunsubstituted fluoroalkylene group having 1 to 5 carbon atoms in whichat least one of C—C bonds is converted into a C—O—C bond; and Brepresents a group selected from a substituted or unsubstituted alkylenegroup having 1 to 5 carbon atoms, a polyfluoroalkylene group having 1 to5 carbon atoms, and a substituted or unsubstituted fluoroalkylene grouphaving 1 to 5 carbon atoms.

From the viewpoint including stability of the compound, easiness ofsynthesis of the compound, solubility in a solvent and cost, A ispreferably a group selected from a substituted or unsubstituted alkylenegroup having 1 to 5 carbon atoms, a polyfluoroalkylene group having 1 to5 carbon atoms, a substituted or unsubstituted fluoroalkylene grouphaving 1 to 5 carbon atoms, a substituted or unsubstituted alkylenegroup having 1 to 5 carbon atoms in which at least one of C—C bonds isconverted into a C—O—C bond, a polyfluoroalkylene group having 1 to 5carbon atoms in which at least one of C—C bonds is converted into aC—O—C bond, and a substituted or unsubstituted fluoroalkylene grouphaving 1 to 5 carbon atoms in which at least one of C—C bonds isconverted into a C—O—C bond. A group selected from a substituted orunsubstituted alkylene group having 1 to 5 carbon atoms, apolyfluoroalkylene group having 1 to 5 carbon atoms, and a substitutedor unsubstituted fluoroalkylene group having 1 to 5 carbon atoms is morepreferable, and a substituted or unsubstituted alkylene group having 1to 5 carbon atoms is still more preferable, and a methylene group, anethylene group or a 2,2-propanediyl group is particularly preferable inthe compound represented by the general formula (3). The fluoroalkylenegroup having 1 to 5 carbon atoms mentioned above preferably includes amethylene group and a difluoromethylene group, and it is more preferablyconsisted of a methylene group and a difluoromethylene group.

For the same reason as above, B is preferably an alkylene group ofhaving 1 to 5 carbon atoms, and more preferably methylene group,1,1-ethanediyl group or 2,2-propanediyl group.

These cyclic sulfonates having two sulfonyl groups are disclosed in thespecification of U.S. Pat. No. 4,950,768. Specific examples of thecompound represented by the general formula (3) are shown below, butthese are not restrictive examples.

These compounds have LUMOs in the similar level to those of the compoundof the general formula (1) of the present invention, and two or moresulfonyl groups, and if Compound No.1 and Compound No.21 (MMDS), forexample, are added in the electrolyte solution, a composite film havinga high ion conductivity can be easily formed at an initial stage ofcharging. MMDS is a cyclic compound and it is supposed that it readilyform a film by reacting with the anode after the ring is opened.

If MMDS contributes to film formation quite selectively on the anode,the film formation probability of Compound No.1 on the anode decreasesand the reaction probability thereof on the cathode increases, and thefilm formation on the cathode is achieved. Consequently, suppression ofthe solvent decomposition on the cathode can be expected.

When the compound of the general formula (3) is added in the electrolytesolution, the content thereof in the electrolyte solution is notparticularly limited but it is preferably contained in an amount of 0.5weight % to 10.0 weight % in the electrolyte solution. The effect maynot be sufficiently exhibited below 0.5 weight % in the film formationthrough electrochemical reaction on the surface of the electrodes. If itexceeds 10.0 weight %, the viscosity of the electrolyte solution mayincrease. The ratio of the compound of the general formula (3) in thecompounds of the general formula (1) and the general formula (3) ispreferably 10 to 90 weight % based on the total weight of the compoundof the general formula (1) and the general formula (3). When thecompound of the general formula (2) is used in addition to them, it ispreferably 10 to 90 weight % based on the total weight of the compoundof the general formula (1), general formula (2) and general formula (3).

In the present invention, in some cases at least one of vinylenecarbonate (VC) and the derivatives thereof can be added in theelectrolyte solution. An improvement of the cycle characteristic can befurther achieved by adding at least one of VC and the derivativesthereof. LUMO of VC is 0.09 eV and it is supposed that it is lesssusceptible to reduction reaction and exists in the electrolyte solutionover a long period of time without being consumed in the reductionreaction at an initial stage of charge/discharge compared with thecompound of the general formula (1). Therefore, it can contribute to theimprovement in the cycle characteristics by being gradually consumed atthe time of charge/discharge cycles. When at least one of the vinylenecarbonate (VC) and the derivatives thereof is used as an additive to theelectrolyte solution, the effect thereof can be obtained by the additionof 0.05 weight % to 3.0 weight % to the electrolyte solution.

When the compound of the general formula (1) and VC, the compound of thegeneral formula (1) and the other additive and VC are further added inthe electrolyte solution, the ratio of VC in the whole electrolytesolution is not particularly limited but it is preferably 0.5 weight %to 10.0 weight %. The effect may not be sufficiently exhibited below 0.5weight % in the film formation through electrochemical reaction on thesurface of the electrodes. If it exceeds 10.0 weight %, the viscosity ofthe electrolyte solution may increase.

The electrolyte solution of the present invention can be provided byadding and dissolving beforehand the compound represented by the generalformula (1) in the electrolyte solution. The desired electrolytesolution can be obtained by adding suitably the other additives (cyclicmonosulfonate, cyclic sulfonate having two sulfonyl groups, sulfolane,alkane sulfonic anhydride, sulfolene compound, or vinylene carbonatecompound) to this electrolyte solution.

The shape of the secondary battery of the present invention is notparticularly limited, and includes a cylinder type, a rectangular type,a coin type, a laminate type, for example. Among these, the laminatetype has a shape sealed in a jacket which consists of a flexible filmcomprising of a laminate of a synthetic resin and a metal foil, and isreadily affected by the increase of inner pressure as compared withthose enclosed in a jacket which consists of a battery can of a cylindertype, a rectangular shape and a coin type, therefore control of chemicalreaction on the interface of the electrodes and the electrolyte solutionis more important. If it is a secondary battery containing a lineardisulfone compound represented by the general formula (1) of the presentinvention, suppression of the increase of resistance, and batteryswelling (due to the generation of gas and increase of inner pressure)is possible even in a laminate type battery. Therefore, it becomespossible to secure safety and reliability over a long period of timeeven in large-sized secondary lithium ion batteries such as those usedin an automobile.

The lithium secondary battery of the present invention can be obtainedby laminating an anode 13 and a cathode 12 with a separator 16positioned therebetween or rolling such a laminate and placing it into ajacket in a dry air or inactive gas atmosphere, and after impregnatingit with an electrolyte solution containing the compound represented by ageneral formula (1), sealing the battery jacket. It is possible toobtain the effect of the present invention by forming the films on theelectrodes by charging a battery before or after sealing.

In addition, the linear disulfonate represented by the general formula(1) of the present invention can be used as an additive of electrolytesolution not only for a lithium secondary battery but also for the otherelectrochemical devices. Examples of the other electrochemical devicesinclude an organic radical battery, a capacitor and a dye sensitizedwet-type solar cell.

EXAMPLES

(Fabrication of Battery)

Cathode active material given in Tables 1 to 5 and a conductivityimparting agent were subjected to dry-type mixing, and uniformlydispersed in N-methyl-2-pyrrolidone (NMP) in which PVDF serving as abinder has been dissolved to prepare a slurry. Carbon black was used asa conductivity imparting agent. The slurry was applied on an aluminummetal foil (20 μm in the case of a cylinder type and 25 μm in the caseof a laminated type) serving as cathode current collector and NMP wasevaporated to form a cathode sheet. The solid content ratio in thecathode was cathode active material: conductivity imparting agent:PVDF=80:10:10 (weight %).

On the other hand, when an anode active material consists of a carbonmaterial, carbon and PVDF are mixed so that carbon: PVDF=90:10 (weight%), dispersed in NMP and applied on a copper foil (10 μm in the case ofa coin type and cylinder type and 20 μm in the case of a laminated type)serving as anode current collector 14.

The electrolyte solutions 15 comprising the solvents given in Tables 1to 5, 1 mol/L of LiPF₆ as an electrolyte and additives given in Tables 1to 5 were used.

After that, cylinder type secondary battery (Examples 1 to 23,Comparative Examples 1 and 2) and the aluminum laminate film typesecondary battery (Examples 24 to 53, Comparative Examples 3 to 11) werefabricated by laminating an anode and a cathode with a separator 16which consists of polyethylene therebetween. In the case of an aluminumlaminate film type secondary battery, the used laminate film had astructure in which polypropylene resin (melt sealing layer, thickness of70 μm), polyethylene terephthalate (20 μm), aluminum (50 μm), andpolyethylene terephthalate (20 μm) were laminated in this order. Thesewere cut into two sheets of a predetermined size, and recessed partswere formed in some parts thereof which had bottom and side portionswhich were suited for the size of the laminate electrode. These werepositioned face to face to enclose the laminate electrode and thecircumference thereof was heat-sealed to form a film jacketed battery.Before the last one side was heat-sealed, the laminate electrode wasimpregnated with an electrolyte solution.

(Charge/Discharge Cycle Test)

The charge rate and discharge rate were adjusted to 1 C respectively,and the charge termination voltage to 4.2 V and the dischargetermination voltage to 2.5 V. The capacity retention ratio is a valueobtained by dividing a discharge capacity (mAh) after 500 cycles by adischarge capacity (mAh) of the tenth cycle.

(Test of Characteristics After Storage)

The characteristics after storage was estimated by the ratio of increasein the resistance after the stored for 60 days at 50% (45° C.) dischargedepth (the ratio of the resistance after storage assuming that theinitial resistance (at the time of beginning storage) was 1; thecharge/discharge conditions were the same as in the charge/dischargecycle test).

TABLE 1 Type and Content of the Additive in the Cathode AnodeElectrolyte solution Solvent Active Material Active Material (weight %)(Volume Ratio) Shape of the Cell Example 1 LiMn₂O₄ Amorphous Carbon No.1(0.5) PC/EC/DEC Cylinder type (20/20/60) Example 2 LiMn₂O₄ AmorphousCarbon No. 2(0.5) PC/EC/DEC Cylinder type (20/20/60) Example 3 LiMn₂O₄Amorphous Carbon No. 3(0.5) PC/EC/DEC Cylinder type (20/20/60) Example 4LiMn₂O₄ Amorphous Carbon No. 4(0.5) PC/EC/DEC Cylinder type (20/20/60)Example 5 LiMn₂O₄ Amorphous Carbon No. 6(0.5) PC/EC/DEC Cylinder type(20/20/60) Example 6 LiMn₂O₄ Amorphous Carbon No. 9(0.5) PC/EC/DECCylinder type (20/20/60) Example 7 LiMn₂O₄ Amorphous Carbon No. 10(0.5)PC/EC/DEC Cylinder type (20/20/60) Example 8 LiMn₂O₄ Amorphous CarbonNo. 15(0.5) PC/EC/DEC Cylinder type (20/20/60) Example 9 LiMn₂O₄Amorphous Carbon No. 19(0.5) PC/EC/DEC Cylinder type (20/20/60) Example10 LiMn₂O₄ Amorphous Carbon No. 16(0.5) PC/EC/DEC Cylinder type(20/20/60) Comparative LiMn₂O₄ Amorphous Carbon None PC/EC/DEC Cylindertype Example 1 (20/20/60) Comparative LiMn₂O₄ Amorphous Carbon 1% 1,3-PSPC/EC/DEC Cylinder type Example 2 (20/20/60)

TABLE 2 Type and Content of the Additive in the Cathode AnodeElectrolyte solution Solvent Active Material Active Material (weight %)(Volume Ratio) Shape of the Cell Example 11 LiMn₂O₄ Amorphous Carbon No.1(0.01) PC/EC/DEC Cylinder type (20/20/60) Example 12 LiMn₂O₄ AmorphousCarbon No. 1(0.05) PC/EC/DEC Cylinder type (20/20/60) Example 13 LiMn₂O₄Amorphous Carbon No. 1(0.075) PC/EC/DEC Cylinder type (20/20/60) Example14 LiMn₂O₄ Amorphous Carbon No. 1(0.1) PC/EC/DEC Cylinder type(20/20/60) Example 15 LiMn₂O₄ Amorphous Carbon No. 1(0.75) PC/EC/DECCylinder type (20/20/60) Example 16 LiMn₂O₄ Amorphous Carbon No. 1(1.0)PC/EC/DEC Cylinder type (20/20/60) Example 17 LiMn₂O₄ Amorphous CarbonNo. 1(2.0) PC/EC/DEC Cylinder type (20/20/60) Example 18 LiMn₂O₄Amorphous Carbon No. 1(3.0) PC/EC/DEC Cylinder type (20/20/60) Example19 LiMn₂O₄ Amorphous Carbon No. 1(5.0) PC/EC/DEC Cylinder type(20/20/60) Example 20 LiMn₂O₄ Amorphous Carbon No. 1(6.0) PC/EC/DECCylinder type (20/20/60) Example 21 LiMn₂O₄ Amorphous Carbon No. 1(7.5)PC/EC/DEC Cylinder type (20/20/60) Example 22 LiMn₂O₄ Amorphous CarbonNo. 1(10.0) PC/EC/DEC Cylinder type (20/20/60) Example 23 LiMn₂O₄Amorphous Carbon No. 1(12.5) PC/EC/DEC Cylinder type (20/20/60)

TABLE 3 Type and Content of the Additive in the Cathode AnodeElectrolyte solution Solvent Active Material Active Material (weight %)(Volume Ratio) Shape of the Cell Example 24 LiMn₂O₄ Graphite No. 1(1.5)PC/EC/DEC Laminate type (20/20/60) Example 25 LiMn₂O₄ Graphite No.1(1.5) +0.5% PC/EC/DEC Laminate type 1,3-PS (20/20/60) Example 26LiMn₂O₄ Graphite No. 1(1.5) +0.5% PC/EC/DEC Laminate type 1,4-BS(20/20/60) Example 27 LiMn₂O₄ Graphite No. 1(1.5) +0.5% PC/EC/DECLaminate type 1,3-PS +0.5% VC (20/20/60) Example 28 LiMn₂O₄ Graphite No.1(1.5) +0.5% PC/EC/DEC Laminate type MMDS (20/20/60) Example 29 LiMn₂O₄Graphite No. 1(1.5) +0.5% PC/EC/DEC Laminate type MMDS +0.5% VC(20/20/60) Comparative LiMn₂O₄ Graphite None PC/EC/DEC Laminate typeExample 3 (20/20/60) Comparative LiMn₂O₄ Graphite +0.5% PC/EC/DECLaminate type Example 4 1,3-PS +1.5% VC (20/20/60)

TABLE 4 Type and Content of the Additive in the Cathode AnodeElectrolyte solution Solvent Active Material Active Material (weight %)(Volume Ratio) Shape of the Cell Example 30 LiMnO₂ Amorphous Carbon No.1(0.5) PC/EC/DEC Laminate type (20/20/60) Example 31 LiMnO₂ AmorphousCarbon No. 2(0.5) PC/EC/DEC Laminate type (20/20/60) Example 32 LiMnO₂Amorphous Carbon No. 3(0.5) PC/EC/DEC Laminate type (20/20/60) Example33 LiMnO₂ Amorphous Carbon No. 4(0.5) PC/EC/DEC Laminate type (20/20/60)Example 34 LiMnO₂ Amorphous Carbon No. 6(0.5) PC/EC/DEC Laminate type(20/20/60) Example 35 LiMnO₂ Amorphous Carbon No. 9(0.5) PC/EC/DECLaminate type (20/20/60) Example 36 LiMnO₂ Amorphous Carbon No. 10(0.5)PC/EC/DEC Laminate type (20/20/60) Example 37 LiMnO₂ Amorphous CarbonNo. 15(0.5) PC/EC/DEC Laminate type (20/20/60) Example 38 LiMnO₂Amorphous Carbon No. 19(0.5) PC/EC/DEC Laminate type (20/20/60) Example39 LiMnO₂ Amorphous Carbon No. 16(0.5) PC/EC/DEC Laminate type(20/20/60) Example 40 LiMnO₂ Amorphous Carbon No. 1(0.05) PC/EC/DECLaminate type (20/20/60) Example 41 LiMnO₂ Amorphous Carbon No. 1(0.1)PC/EC/DEC Laminate type (20/20/60) Example 42 LiMnO₂ Amorphous CarbonNo. 1(1.0) PC/EC/DEC Laminate type (20/20/60) Example 43 LiMnO₂Amorphous Carbon No. 1(3.0) PC/EC/DEC Laminate type (20/20/60) Example44 LiMnO₂ Amorphous Carbon No. 1(5.0) PC/EC/DEC Laminate type (20/20/60)Example 45 LiMnO₂ Amorphous Carbon No. 1(6.0) PC/EC/DEC Laminate type(20/20/60) Example 46 LiMnO₂ Amorphous Carbon No. 1(7.5) PC/EC/DECLaminate type (20/20/60) Example 47 LiMnO₂ Amorphous Carbon No. 1(10.0)PC/EC/DEC Laminate type (20/20/60)

TABLE 5 Type and Content of the Additive in the Cathode AnodeElectrolyte solution Solvent Active Material Active Material (weight %)(Volume Ratio) Shape of the Cell Example 48 LiMnO₂ Amorphous Carbon No.1(0.5) +0.5 PC/EC/DEC Laminate type %1,3-PS (20/20/60) Example 49 LiMnO₂Amorphous Carbon No. 1(0.5) +0.5 PC/EC/DEC Laminate type %1,4-BS(20/20/60) Example 50 LiMnO₂ Amorphous Carbon No. 1(0.5) +0.5% PC/EC/DECLaminate type MMDS (20/20/60) Example 51 LiMnO₂ Amorphous Carbon No.1(0.5) +0.5% PC/EC/DEC Laminate type MMDS +0.5% VC (20/20/60) Example 52LiMnO₂ Amorphous Carbon No. 1(0.5) +0.5% PC/EC/DEC Laminate type 1,3-PS+0.5% VC (20/20/60) Example 53 LiMnO₂ Amorphous Carbon No. 1(0.5) +0.5%PC/EC/DEC Laminate type 1,4-BS +0.5% VC (20/20/60) Comparative LiMnO₂Amorphous Carbon None PC/EC/DEC Laminate type Example 5 (20/20/60)Comparative LiMnO₂ Amorphous Carbon 0.5% 1,3-PS PC/EC/DEC Laminate typeExample 6 (20/20/60) Comparative LiMnO₂ Amorphous Carbon 0.5% 1,4-BSPC/EC/DEC Laminate type Example 7 (20/20/60) Comparative LiMnO₂Amorphous Carbon 0.5% MMDS PC/EC/DEC Laminate type Example 8 (20/20/60)Comparative LiMnO₂ Amorphous Carbon 0.5% 1,3-PS +0.5% PC/EC/DEC Laminatetype Example 9 VC (20/20/60) Comparative LiMnO₂ Amorphous Carbon 0.5%1,4-BS +0.5% PC/EC/DEC Laminate type Example 10 VC (20/20/60)Comparative LiMnO₂ Amorphous Carbon 0.5% MMDS +0.5% PC/EC/DEC Laminatetype Example 11 VC (20/20/60)

“No.” in the “Type and Content of the Additive in the Electrolytesolution” column in Tables 1 to 5 refers to Compound No.

In addition, the results obtained by the cycle test and the test afterstorage are shown in the following Tables 6 to Table 10. The resistanceincrease ratio in the characteristics after storage is a relative valueassuming that the initial value is 1.

TABLE 6 Characteristics after Capacity retention Storage (Resistanceratio (%) at 500 cycle Increase Ratio) Example 1 90.1 1.055 Example 289.8 1.082 Example 3 90.4 1.078 Example 4 90.5 1.077 Example 5 90.11.061 Example 6 89.3 1.089 Example 7 88.4 1.095 Example 8 86.6 1.068Example 9 86.4 1.066 Example 10 85.9 1.078 Comparative 76.4 1.512Example 1 Comparative 80.9 1.384 Example 2

TABLE 7 Characteristics after Capacity retention Storage (Resistanceratio (%) at 500 cycle Increase Ratio) Example 11 80.1 1.213 Example 1281.5 1.209 Example 13 82.6 1.193 Example 14 87.8 1.098 Example 15 90.81.069 Example 16 90.7 1.055 Example 17 90.6 1.089 Example 18 90.3 1.078Example 19 90.0 1.081 Example 20 85.5 1.123 Example 21 82.6 1.135Example 22 81.9 1.165 Example 23 81.5 1.198

TABLE 8 Characteristics after Storage (Resistance Increase Ratio)Capacity retention Resistance Capacity Change in ratio (%) at IncreaseRecovery Cell Volume × 500 cycle Ratio Ratio(%) 10⁻⁶(m³) Example 24 89.21.089 90.6 0.22 Example 25 91.2 1.068 89.1 0.12 Example 26 91.0 1.08288.7 0.14 Example 27 92.9 1.053 88.4 0.18 Example 28 91.1 1.102 91.10.16 Example 29 92.8 1.068 90.1 0.20 Comparative 77.4 1.526 79.4 0.63Example 3 Comparative 81.3 1.298 82.1 0.34 Example 4

TABLE 9 Characteristics after Capacity retention Storage (Resistanceratio (%) at 500 cycle Increase Ratio) Example 30 87.5 1.109 Example 3186.2 1.125 Example 32 88.1 1.106 Example 33 87.6 1.138 Example 34 87.91.126 Example 35 86.5 1.165 Example 36 86.0 1.155 Example 37 85.2 1.135Example 38 85.1 1.144 Example 39 85.6 1.138 Example 40 80.3 1.256Example 41 84.7 1.187 Example 42 87.1 1.138 Example 43 86.8 1.135Example 44 87.5 1.142 Example 45 82.3 1.186 Example 46 81.6 1.203Example 47 80.9 1.239

TABLE 10 Characteristics after Capacity retention Storage (Resistanceratio (%) at 500 cycle Increase Ratio) Example 48 89.2 1.083 Example 4988.9 1.088 Example 50 89.1 1.091 Example 51 91.1 1.056 Example 52 90.91.053 Example 53 90.7 1.059 Comparative 76.3 1.516 Example 5 Comparative80.6 1.346 Example 6 Comparative 80.2 1.389 Example 7 Comparative 79.51.378 Example 8 Comparative 81.9 1.298 Example 9 Comparative 81.3 1.268Example 10 Comparative 81.6 1.274 Example 11(Effect by Addition of the Compound of the General Formula (1))

The capacity retention ratios in Examples 1 to 10 and Examples 30 to 39are respectively compared with those in Comparative Examples 1 and 2,and 5 to 11, a significant improvement in the cycle characteristics andextensive control of the characteristics after storage were confirmed inExamples 1 to 10 and Examples 30 to 39. In addition, as for thebatteries shown in Examples 1 to 10 and Examples 30 to 39, the anode andcathode surfaces after cycle test were investigated with X-rayphotoelectron spectroscopy (XPS) and energy dispersive X-ray analysis(EDX), which revealed the existence of LiF, LiCO₃, etc. Furthermore, asa result of performing peak division of the sulfur spectrum by XPSanalysis, it was confirmed that the substance having a peak near 164 eVexisted in both the cathode and anode. There was no substance having apeak near 164 eV in each of the cathode and anode in Comparative Example1 and in the cathode of the system using an additive in ComparativeExample 2, and it is supposed that a film peculiar to the lineardisulfone acid of the present invention was formed.

(Influence of the Concentration of the Compound of the General Formula(1) in Electrolyte Solution)

The concentration of Compound No.1 occupied in the electrolyte solutionwas varied in Examples 11 to 23 and Examples 40 to 47, and thefabricated secondary batteries were evaluated. The capacity retentionratio after 500 cycles decreased when the concentration was below 0.1weight % and exceeded 5.0 weight %. Moreover, it turned out that theresistance increase ratio after 60 days storage increased when theconcentration was below 0.1 weight % and exceeded 5.0 weight %. Fromthis result, it has been confirmed that the concentration of thecompound of the general formula (1) in the electrolyte solution ispreferably 0.1 weight % to 5.0 weight %, and the particularly preferableconcentration range is 0.5 weight % to 3.0 weight %.

(Evaluation of Characteristics of Laminate Film Type Battery)

Laminated type batteries of Examples 24 to 29 and Comparative Examples 3and 4 were used and they were charged with a constant current of 2A anda constant voltage for 5 hours to termination voltage 4.3 V at roomtemperature (25° C.), and then discharged with a constant current of 2Ato termination voltage 2.5V, and the generated gas was removed and thevolume of the battery at this time was measured. After the gas wasremoved and the batteries were left standing for one week, they werecharged and discharged one time again respectively at room temperature.The charge current and discharge current at this time were fixed (2 A),and the discharge capacity at this time was regarded as the initialcapacity. The cutoff potential on the side of discharge was adjusted to2.5 V and the cutoff potential on the side of charge was adjusted to 4.3V. Then, after charged for 2.5 hours to 4.2 V with a constant current of2 A and a constant voltage, the batteries were discharged to 50% ofdischarge depth and left standing at 55° C. for 84 days. After thebatteries were left standing, discharging operations were againperformed with a constant current at room temperature, and then chargingand discharging were similarly repeated with a constant current one moretime, and the discharge capacity at this time was regarded as recoverycapacity. Here, the ratio of capacity recovery was determined as(recovery capacity)/(initial capacity). The volumes of batteries weremeasured simultaneously and the difference with the volume immediatelyafter the gas was removed was regarded as the amount of cell volumechange.

In addition, as for the laminated type batteries of Examples 24 to 47and Comparative Examples 3 to 11, the resistance increase rate and thecapacity retention ratio after 500 cycles were measured.

(Effect of the Addition of the Compound of the General Formula (1) in aLaminate Film Type Battery)

The ratio of capacity recovery after the storage and the capacityretention ratio after 500 cycles in Example 24 and the capacityretention ratio after the 500 cycles in Examples 30 to 47 were greatlyimproved as compared with those in Comparative Example 3 and ComparativeExample 5 in which the compound of the general formula (1) was notadded. In addition, the resistance increase rate after storage wasgreatly suppressed as compared with those in Comparative Example 3 andComparative Example 5 in which the compound was not added. These resultsare considered to be resulted from the fact that a film having higherion conductivity and high stability after storage as compared withadditive-free systems or conventional additive systems was formed by theaddition of the compound represented by the general formula (1) of thepresent invention in the electrolyte solution. Furthermore, as for theamount of volume change of the laminate jacket cell after storage, theamount of volume change of the cell of Example 24 is smaller than thatin Comparative Example 3 and Comparative Example 4. This is consideredto be attributable to the fact that decomposition film of compound (1)was formed on the electrode and suppressed the generation of gasresulted from decomposition of the electrolyte solution.

(Effect of the Addition of the Cyclic Monosulfonate in a Laminate FilmType Battery)

The amount of cell volume change in Example 25 and Example 26 is smallerthan that in Comparative Example 3, Comparative Example 4 and Example24. This is considered to be attributable to the composite effect of thecompound (1) and 1,3-PS or 1,4-BS, which formed a film on the anode andgreatly suppressed the generation of gas resulted from decomposition ofthe electrolyte solution.

(Effect of the Addition of the Cyclic Sulfonate Having two SulfonylGroups in a Laminate Film Type Battery)

The ratio of capacity recovery and the capacity retention ratio after500 cycles in Example 28 were further improved as compared with Example24. The capacity retention ratio after the 500 cycles in Example 50 wasalso further improved as compared with Example 30. These results areconsidered to be resulted from the fact that a film having higher ionconductivity and high stability after storage as compared withadditive-free systems or conventional additive systems was formed by theaddition of the compound represented by the general formula (1) of thepresent invention and the cyclic sulfonate having two sulfonyl groups inthe electrolyte solution. The amount of volume change of the cell inExample 28 is smaller than that in Comparative Example 3, ComparativeExample 4, and Example 24. This is considered to be attributable to thecomposite effect of the compound (1) and MMDS, which formed a film onthe anode and greatly suppressed the generation of gas resulted fromdecomposition of the electrolyte solution.

(Effect of the Addition of VC in a Laminate Film Type Battery)

The cycle characteristics of the cell in Examples 27, 52 and 53 werefurther improved as compared with Examples 25, 48 and 49. These resultsare considered to be resulted from the fact that a film having higherion conductivity and high stability after storage or charge/dischargecycles as compared with additive-free systems or conventional additivesystems was formed by the addition of the compound represented by thegeneral formula (1) of the present invention and the cyclicmonosulfonate and vinylene carbonate in the electrolyte solution. Inaddition, the cycle characteristics of the cell in Examples 29 and 51were improved as compared with Examples 28 and 50. These results areconsidered to be resulted from the fact that a film having higher ionconductivity and high stability after storage or charge/discharge cyclesas compared with additive-free systems or conventional additive systemswas formed by the addition of the compound represented by the generalformula (1) of the present invention and the cyclic sulfonate having twosulfonyl groups and vinylene carbonate in the electrolyte solution.

The invention claimed is:
 1. An additive for an electrolyte solution foran electrochemical device, said additive comprising a compoundrepresented by the following formula:

wherein R₁ and R₄ are each independently selected from the groupconsisting of a substituted or unsubstituted alkyl group having 1 to 5carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1to 5 carbon atoms, a polyfluoroalkyl group having 1 to 5 carbon atoms,—SO₂X₁, wherein X₁ is a substituted or unsubstituted alkyl group having1 to 5 carbon atoms, —SY₁, wherein Y₁ is a substituted or unsubstitutedalkyl group having 1 to 5 carbon atoms, and —COZ, wherein Z is ahydrogen atom or a substituted or unsubstituted alkyl group having 1 to5 carbon atoms; R₂ and R₃ are each independently selected from the groupconsisting of an unsubstituted alkyl group having 1 and 3 to 5 carbonatoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbonatoms, a substituted or unsubstituted phenoxy group, an unsubstitutedfluoroalkyl group having 1 to 5 carbon atoms, a substituted orunsubstituted fluoroalkoxy group having 1 to 5 carbon atoms, apolyfluoroalkoxy group having 1 to 5 carbon atoms, a halogen atom,—NX₂X₃, wherein X₂ and X₃ independently represent a hydrogen atom or asubstituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and—NY₂CONY₃Y₄, wherein Y₂ to Y₄ independently represent a hydrogen atom ora substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.